1. Field of the Invention
This invention relates to a process for mild hydrocracking of heavy oils. More particularly, this invention relates to a catalytic process for converting heavy oils boiling above 650.degree. F., such as vacuum gas oil (VGO) and VGO containing a high proportion of vacuum resid (VR) to lighter distillate products boiling at or below 650.degree. F.
In the mild hydrocracking process of this invention a sulfur- and metal-containing hydrocarbon feedstock, such as residua containing heavy oils, is contacted at an elevated temperature with hydrogen and a catalyst composition comprising a specified amount of a Group VIII metal, such as an oxide of nickel or cobalt, a specified amount of an oxide of molybdenum and, optionally, a specified amount of an oxide of phosphorus, such as phosphorus pentoxide supported on a porous silica-containing alumina support. In the catalytic mild hydrocracking process of this invention the sulfur- and metal-containing hydrocarbon feed is contacted with hydrogen and the catalyst, which has a specified pore size distribution, in a manner such that a substantially higher conversion of the 1000.degree. F.+ fraction of the hydrocarbon feed to the 1000.degree. F.- lighter products is achieved over that obtained with the use of prior art hydroprocessing catalysts while at the same time high levels of sediment formation are avoided.
2. Prior Art
U.S. Pat. No. 4,941,964, incorporated herein by reference, discloses a process for the hydrotreatment of a sulfur- and metal-containing hydrocarbon feed which comprises contacting the feed with hydrogen and a catalyst in a manner such that the catalyst is maintained at isothermal conditions and is exposed to a uniform quality of feed. The catalyst has a composition comprising 3.0-5.0 wt. % of an oxide of a Group VIII metal, 14.5-24.0 wt. % of an oxide of a Group VIB metal and 0-2.0 wt. % of an oxide of phosphorus supported on a porous alumina support, and the catalyst is further characterized by having a total surface area of 150-210 m.sup.2 /g and a total pore volume (TPV) of 0.50-0.75 cc/g with a pore diameter distribution such that micropores having diameters of 100-160 .ANG. constitute 70-85% of the total pore volume of the catalyst and macropores having diameters of greater than 250 .ANG. constitute 5.5-22.0% of the total pore volume of the catalyst.
U.S. Pat. No. 4,670,132 (Arias, et al.) discloses a catalyst preparation and a catalyst composition useful in the hydroconversion of heavy oils, the catalyst comprising a high iron content bauxite with the addition of one or more of the following promoters: phosphorus, molybdenum, cobalt, nickel or tungsten. The bauxite catalysts typically contain 25-35 wt. % aluminum. The catalysts have certain characteristic features for the elemental components (including aluminum and where present, molybdenum) when the pellet exteriors are examined in the fresh oxide state using X-ray photoelectron spectroscopy (XPS). For those catalysts which contain molybdenum, the surface Mo/Al atomic ratios on the pellet exteriors are in the range of 0.03 to 0.09.
U.S. Pat. No. 4,652,545 (Lindsley, et al.) discloses a catalyst composition useful in the hydroconversion of heavy oils, the catalyst containing 0.5-5% Ni or Co and 1.8-18% Mo (calculated as the oxides) on a porous alumina support, such as alumina containing a minor amount of silica, having 15-30% of the Ni or Co in an acid extractable form, and further characterized by having a TPV of 0.5-1.5 cc/g with a pore diameter distribution such that (i) at least 70% TPV is in pores having 80-120 .ANG. diameters, (ii) less than 0.03 cc/g of TPV (6% TPV) is in pores having diameters of less than 80 .ANG. and (iii) 0.05-0.1 cc/g of TPV (3-20% TPV) is in pores having diameters of greater than 120 .ANG.. Lindsley, et al. is distinguished from the instant invention in that although it teaches that having a proportion of nickel or cobalt contained in its catalyst in an acid extractable form is advantageous in terms of heavy oil hydroconversion. Lindsley, et al. does not teach or suggest that catalysts which have a prescribed molybdenum gradient are advantageous in terms of heavy oil hydroconversion.
U.S. Pat. No. 4,588,709 (Morales, et al.) discloses a catalyst preparation and a catalyst composition useful in the hydroconversion of heavy oils, the catalyst comprising 5-30 wt. % of a Group VIB element (e.g., molybdenum) and 1-5 wt. % of a Group VIII element (e.g., nickel). Morales, et al. indicate that the finished catalysts have average pore diameters of 150 to 300 Angstroms. The catalysts have certain characteristic features for the active components (Mo and Ni) when the pellet exteriors are examined in a sulfided state using X-ray photoelectron spectroscopy (XPS). Morales ('709) requires a large average pore diameter (150 to 300 Angstroms) and Morales ('709) requires certain characteristic XPS features of the pellet exteriors after presulfiding.
U.S. Pat. No. 4,579,649 (Morales, et al.) discloses a catalyst preparation and a catalyst composition useful in the hydroconversion of heavy oils, the catalyst containing a Group VIB element (e.g., molybdenum), a Group VIII element (e.g., nickel) and phosphorus oxide on a porous alumina support. The catalyst has certain characteristic features for the three active components (Mo, Ni and P) where the pellet exteriors are examined in a sulfided state using X-ray photoelectron spectroscopy (XPS). Morales ('649) requires certain characteristic XPS features of the pellet exteriors after presulfiding whereas the catalyst of the instant invention requires a specified molybdenum gradient as determined by measuring the molybdenum/aluminum atomic ratios by XPS for catalyst pellet exteriors and the pellets in a crushed form as measured on the fresh catalysts in an oxide state.
U.S. Pat. No. 4,520,128 (Morales, et al.) discloses a catalyst preparation and a catalyst composition useful in the hydroconversion of heavy oils, the catalyst containing 5-30 wt. % of a Group VIB element (e.g., molybdenum), 0.1-8.0 wt. % of a Group VIII element (e.g., nickel) and 5-30 wt. % of a phosphorus oxide on a porous alumina support. The finished catalysts of Morales ('128) have mean pore diameters of 145 to 154 Angstroms. The catalyst has certain characteristic features for the three active components (Mo, Ni and P) when the pellet exteriors are examined in a sulfided state using X-ray photoelectron spectroscopy (XPS). The catalyst of Morales requires a high phosphorus oxide content.
U.S. Pat. No. 5,047,142 (Sherwood, Jr., et al.) discloses a process of hydroprocessing a sulfur- and metal-containing hydrocarbon feed which comprises contacting said feed with hydrogen and a catalyst in a manner such that the catalyst is maintained at isothermal conditions and is exposed to a uniform quality of feed, where said catalyst has a composition comprising 1.0-5.0 wt. % of an oxide of nickel or cobalt and 10.0-25.0 wt. % of an oxide of molybdenum, all supported on a porous alumina support in such a manner that the molybdenum gradient of the catalyst has a value of less than 6.0, 15-30% of the nickel or cobalt is in an acid extractable form, and said catalyst is further characterized by having a total surface area of 150-210 m.sup.2 /g, a total pore volume of 0.50-0.75 cc/g, and a pore size distribution such that pores having diameters of less than 100 .ANG. constitute less than 25.0%, pores having diameters of 100-160 .ANG. constitute 70.0-85.0% and pores having diameters of greater than 250 .ANG. constitute 1.0-15.0% of the total pore volume of said catalyst.
U.S. Pat. No. 4,886,582 (Simpson) discloses a catalyst comprising at least one metal hydrogenating component comprising Group VIB, such as molybdenum, or Group VIII metal, such as nickel, on a porous refractory oxide, such as lithia-alumina, silicaalumina, etc., said composition comprising less than 15 wt. % of said metal hydrogenation component calculated as the trioxide, and having a pore size distribution where at least 75% of the total pore volume is in pores of diameters from about 20 Angstroms below the pore mode diameter to about 20 Angstroms above the pore mode diameter, less than 10% of the total pore volume is in pores of diameters less than 60 Angstroms and greater than 3% to less than 10% of the total pore volume is in pores greater than 110 Angstroms and the pore mode diameter is in the range of about 70 to about 90 Angstroms.
U.S. Pat. No. 4,846,961 (Robinson, et al.) discloses a hydroprocessing catalyst containing nickel, phosphorus and about 19 to about 21.5 wt. % of molybdenum (MoO.sub.3) components on a porous refractory oxide such as silica-alumina. The catalyst has a narrow pore size distribution wherein at least 75% of the pore volume is in pores of diameters from about 50 to about 110 Angstroms, at least 10% of the pore volume in pores of diameters less than 70 Angstroms and at least 60% of the pore volume in pores of diameters within about 20 Angstroms above or below the average pore diameter. The catalyst is employed to hydroprocess a hydrocarbon oil, especially those oils containing sulfur and nitrogen components.
U.S. Pat. No. 4,686,030 (Ward, et al.) discloses a mild hydrocracking process using a catalyst containing at least one active hydrogenation metal component supported on an amorphous porous refractory oxide such as silica-alumina wherein the catalyst has a narrow pore size distribution including at least 75% of the total pore volume in pores of diameters from about 50 to about 130 Angstroms. Preferably, the catalyst has at least about 60% of the pore volume in pores of diameter within about 20 Angstroms above or below a mode pore diameter in the range from about 55 to about 100 Angstroms. In one embodiment, a vacuum gas hydrocarbon oil is mildly hydrocracked, with simultaneous desulfurization and denitrogenation, by contact with the catalyst under mild hydrocracking conditions correlated so as to convert about 10 to about 50 Vol % of the oil fraction boiling above 700.degree. F. to hydrocarbon products boiling at or below about 700.degree. F. In other embodiments, the hydrocarbon oil may be desulfurized and denitrogenated either prior to or following the mild hydrocracking.